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The corresponding reaction to produce esters is, however, less developed, as the reaction is generally limited to simple, primary alcohols that are used in solvent\u2010level quantities, thereby restricting the complexity of esters that can be directly formed. Herein, we detail the development of a general ester\u2010forming haloform coupling reaction using one equivalent of alcohol. Mechanistic and kinetic modelling studies demonstrated that the key intermediates are formed under equilibrium, which facilitated the development of conditions that are amenable to secondary alcohols.<\/jats:p>","DOI":"10.1002\/anie.202400570","type":"journal-article","created":{"date-parts":[[2024,3,27]],"date-time":"2024-03-27T10:33:37Z","timestamp":1711535617000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":5,"title":["A Stoichiometric Haloform Coupling for Ester Synthesis with Secondary Alcohols"],"prefix":"10.1002","volume":"63","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-5546-9488","authenticated-orcid":false,"given":"Albert C.","family":"Rowett","sequence":"first","affiliation":[{"name":"School of Chemistry University of Bristol  Cantock's Close Bristol BS8 1TS UK"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-1966-9156","authenticated-orcid":false,"given":"Stephen G.","family":"Sweeting","sequence":"additional","affiliation":[{"name":"School of Chemistry University of Bristol  Cantock's Close Bristol BS8 1TS UK"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3005-8222","authenticated-orcid":false,"given":"David M.","family":"Heard","sequence":"additional","affiliation":[{"name":"School of Chemistry University of Bristol  Cantock's Close Bristol BS8 1TS UK"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2019-7421","authenticated-orcid":false,"given":"Alastair J. 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Therefore aliquots were taken and quenched using a NH4Cl(aq) work-up which was established as a reliable technique to accurately ascertain the concentrations of the reactive intermediates."},{"key":"e_1_2_3_44_1","doi-asserted-by":"crossref","unstructured":"Iodo-7\u2009aand diiodoacetophenone8\u2009aintermediates which have previously been reported as challenging to isolate (A. Zall D. Bensinger B. Schmidt Eur. J. Org. Chem.2012 2012 1439\u20131447) were prepared isolated and characterised. However triiodoacetophenones are much less stable and have not previously been isolated and\/or characterised. We were unable to isolate the highly reactive9\u2009a which was instead tentatively assigned based on its expected19F NMR chemical shift and how its concentration profile maps with the overall mass balance of each reaction.","DOI":"10.1002\/ejoc.201101835"},{"key":"e_1_2_3_45_1","doi-asserted-by":"publisher","DOI":"10.1002\/ejoc.202001118"},{"key":"e_1_2_3_46_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.7b02569"},{"key":"e_1_2_3_47_1","doi-asserted-by":"publisher","DOI":"10.1016\/0040-4039(96)00986-0"},{"key":"e_1_2_3_48_1","doi-asserted-by":"publisher","DOI":"10.1139\/v96-190"},{"key":"e_1_2_3_49_1","doi-asserted-by":"publisher","DOI":"10.1139\/v88-237"},{"key":"e_1_2_3_50_1","unstructured":"Removing the iodide from DBU\u2009\u22c5\u2009HI through the formation of an insoluble metal iodide salt with an inexpensive inorganic base should also aid the formation and reaction of triiodo9\u2009a. We tested this hypothesis by monitoring the reaction of secondary alcohol4\u2009aunder the primary alcohol conditions but with added K2CO3or Ag2CO3(both 3\u2005equiv. see SI). A small increase in the yield of ester5\u2009awith K2CO3suggested that its addition may have the desired effect but that the extent of this effect is limited by the poor solubility of K2CO3in the reaction mixture. 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